US3445435A - Polymerisation of conjugate dienes - Google Patents

Polymerisation of conjugate dienes Download PDF

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Publication number
US3445435A
US3445435A US528360A US3445435DA US3445435A US 3445435 A US3445435 A US 3445435A US 528360 A US528360 A US 528360A US 3445435D A US3445435D A US 3445435DA US 3445435 A US3445435 A US 3445435A
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United States
Prior art keywords
polymerisation
emulsion
content
initiator
trans
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Expired - Lifetime
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US528360A
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English (en)
Inventor
Adrien Azoulay
Jean Teitgen
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Societe Nationale des Petroles dAquitaine SA
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Societe Nationale des Petroles dAquitaine SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/922—Polymerization process of ethylenic monomers using manipulative technique

Definitions

  • the present invention provides the desired improvement. It is possible thereby very considerably to lower the 1,2-vinyl structure in the polymeric substance obtained from a conjugate diene, while it also makes it possible to increase very considerably the proportion of the 1,4-cis stucture at the expense of the 1,4-trans structure, the content of which is lowered.
  • the improvement according to the present invention consists primarily in carrying out the emulsion polymerisation with the gradual introduction of the initiator in the course of the polymerisation.
  • this introduction of the initiator takes place continuously and with a supply decreasing as a function of time.
  • the proportion of initiator introduced at the beginning of the polymerisation only constitutes a fraction of the total necessary quantity of catalyst, but it is greater than the quantities thereafter added.
  • the quantity of initiator introduced into the emulsion at each instant is lower than the quantity added at a preceding instant.
  • the part played by this factor is rather surprising, because it has hitherto been accepted that, with a given systern, the microstructure and the molecular distribution of the polymer were scarcely affected by the proportion 3,445,435 Patented May 20, 1969 "ice of catalyst and consequently by the speed of polymerisation.
  • the present invention arises out of the unexpected observation that the distribution of the 1,2-vinyl, 1,4- trans and 1,4-cis structures is greatly influenced by the mode and speed of introduction of the catalysts, and not only by the temperature of the medium. While in accordance with the earlier knowledge it was necessary to lower the temperature of the medium from C. to 20 Ci in order to be able to reduce the 1,2-viny1 structure content from 25% to 19%, it is possible by the process of the invention to lower this content to the neighbourhood of 15% at reasonable and practical temperatures, notably from 0 to 10 C.
  • the introduction of the initiator as a function of time in accordance with the process of the invention is preferably so adjusted that, during the first hour of the polymerisation, from 20% to 30% of the required total quantity of initiator is introduced, preferably continuously, and the rate of supply is gradually lowered, so as finally to represent only 1% to 2% during the last hour of the operation.
  • the curve of these variations in the rate of supply follows an approximate exponential law whose ordinates are the times and Whose abscissae are the quantities of initiator introduced.
  • the quantities of initiator introduced during each hour of the polymerisation in the case of an operation lasting 12 hours are in the following ratios:
  • the introduction curve is defined by the following ratios:
  • the improvement according to the invention may be applied to polymerisation carried out at various temperatures, with diiferent catalysts, modifiers, emulsifiers, etc., its industrial value is particularly great when operating at temperatures of the order of 2 to 20 C. and above all between 0 and 10 C., particularly in the neighborhood of +5 C.
  • the modifier employed is terdodecylmercaptan.
  • a process for the emulsion polymerization of conjugate dienes comprising the addition to the emulsion of an organic peroxide catalyst jointly with a reducing agent during the polymerization, the improvement which consists in controlling said addition in such a way that the rates at which the organic peroxide and of the reducing agent are introduced into the emulsion always decrease from the beginning to the end of the polymerization, whereby the proportion of 1,4-trans and 1,2-vinyl structures of the polymer produced are lowered, while the amount of 1,4-cis structure is substantially increased.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
US528360A 1965-02-24 1966-02-18 Polymerisation of conjugate dienes Expired - Lifetime US3445435A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR6754A FR1437472A (fr) 1965-02-24 1965-02-24 Perfectionnement à la polymérisation de diènes conjugués

Publications (1)

Publication Number Publication Date
US3445435A true US3445435A (en) 1969-05-20

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US528360A Expired - Lifetime US3445435A (en) 1965-02-24 1966-02-18 Polymerisation of conjugate dienes

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US (1) US3445435A (is")
BE (1) BE676944A (is")
CS (1) CS174102B2 (is")
FR (1) FR1437472A (is")
GB (1) GB1077337A (is")
LU (1) LU50505A1 (is")
NL (1) NL147748B (is")

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100036074A1 (en) * 2008-08-08 2010-02-11 E. I. Du Pont De Nemours And Company Melt-Flowable Fluoropolymer Comprising Repeating Units Arising from Tetrafluoroethylene and a Hydrocarbon Monomer Having a Functional Group and a Polymerizable Carbon-Carbon Double Bond
US20100036073A1 (en) * 2008-08-08 2010-02-11 E. I. Du Pont De Nemours And Company Non-Melt-Flowable Perfluoropolymer Comprising Repeating Units Arising From Tetrafluoroethylene and a Monomer Having a Functional Group and a Polymerizable Carbon-Carbon Double Bond
US20100036053A1 (en) * 2008-08-08 2010-02-11 E.I. Du Pont De Nemours And Company Aqueous Polymerization Process for the Manufacture of Fluoropolymer Comprising Repeating Units Arising from a Perfluoromonomer and a Monomer Having a Functional Group and a Polymerizable Carbon-Carbon Double Bond
US20100034919A1 (en) * 2008-08-08 2010-02-11 E. I. Du Pont De Nemours And Company Melt Processible Semicrystalline Fluoropolymer having Repeating Units Arising from Tetrafluoroethylene, Hexafluoropropylene, and Hydrocarbon Monomer Having a Carboxyl Group and a Polymerizable Carbon-Carbon Double Bond and Multi-Layer Articles Comprising a Layer of the Melt Processible Semicrystalline Fluoropolymer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3507825A1 (de) * 1985-03-06 1986-09-11 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung toluolloeslicher, schwefelmodifizierter chloroprenpolymerisate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3007903A (en) * 1956-04-16 1961-11-07 Dow Chemical Co Continuous polymerization process
US3049519A (en) * 1949-06-27 1962-08-14 Phillips Petroleum Co Emulsion polymerization in the presence of a catalyst comprising an arylcyclohexane hydroperoxide
CA671683A (en) * 1963-10-01 P. Smith Homer Emulsion polymerization
US3317918A (en) * 1956-08-21 1967-05-02 Firestone Tire & Rubber Co Butadiene polymers prepared with a lithium based catalyst characterized by having at least 29 percent of the butadiene as cis-1, 4

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA671683A (en) * 1963-10-01 P. Smith Homer Emulsion polymerization
US3049519A (en) * 1949-06-27 1962-08-14 Phillips Petroleum Co Emulsion polymerization in the presence of a catalyst comprising an arylcyclohexane hydroperoxide
US3007903A (en) * 1956-04-16 1961-11-07 Dow Chemical Co Continuous polymerization process
US3317918A (en) * 1956-08-21 1967-05-02 Firestone Tire & Rubber Co Butadiene polymers prepared with a lithium based catalyst characterized by having at least 29 percent of the butadiene as cis-1, 4

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100036074A1 (en) * 2008-08-08 2010-02-11 E. I. Du Pont De Nemours And Company Melt-Flowable Fluoropolymer Comprising Repeating Units Arising from Tetrafluoroethylene and a Hydrocarbon Monomer Having a Functional Group and a Polymerizable Carbon-Carbon Double Bond
US20100036073A1 (en) * 2008-08-08 2010-02-11 E. I. Du Pont De Nemours And Company Non-Melt-Flowable Perfluoropolymer Comprising Repeating Units Arising From Tetrafluoroethylene and a Monomer Having a Functional Group and a Polymerizable Carbon-Carbon Double Bond
US20100036053A1 (en) * 2008-08-08 2010-02-11 E.I. Du Pont De Nemours And Company Aqueous Polymerization Process for the Manufacture of Fluoropolymer Comprising Repeating Units Arising from a Perfluoromonomer and a Monomer Having a Functional Group and a Polymerizable Carbon-Carbon Double Bond
US20100034919A1 (en) * 2008-08-08 2010-02-11 E. I. Du Pont De Nemours And Company Melt Processible Semicrystalline Fluoropolymer having Repeating Units Arising from Tetrafluoroethylene, Hexafluoropropylene, and Hydrocarbon Monomer Having a Carboxyl Group and a Polymerizable Carbon-Carbon Double Bond and Multi-Layer Articles Comprising a Layer of the Melt Processible Semicrystalline Fluoropolymer

Also Published As

Publication number Publication date
FR1437472A (fr) 1966-05-06
GB1077337A (en) 1967-07-26
NL6602111A (is") 1966-08-25
NL147748B (nl) 1975-11-17
CS174102B2 (is") 1977-03-31
LU50505A1 (is") 1966-08-22
BE676944A (is") 1966-08-23
DE1645323A1 (de) 1970-10-22
DE1645323B2 (de) 1976-01-22

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